The present invention relates to a glass etching liquid or gel composition comprising ammonium bifluoride, a water-miscible organic solvent and water, in which no hydrofluoric acid is contained and a concentration of the ammonium bifluoride is relatively low. Further, the present invention relates to a frosting method therewith for a glass surface, whereby a glass surface in any shapes, i.e., flat, curved, or tubular shapes is easily frosted.
A conventional etching composition for frosting a glass surface typically contains hydrofluoric acid, sulfuric acid or nitric acid. In recent years, an attempt has been made to avoid the use of hydrofluoric acid which has been a fundamental cause for the problems of health hazard and of environmental pollution.
For example, Japanese Patent Publication No. Hei 8-5694 discloses a glass etching composition comprising ammonium bifluoride, water, ferric chloride, sucrose and glycerin.
However, the glass etching composition needs 25 to 35% by weight of ammonium bifluoride, and further comprises 90% by weight of glycerin as a solvent, 12 to 26% by weight of sucrose as a flow modifier and 3.5 to 7.5% by weight of ferric chloride as an activator. Glycerin may be used to form a film on a glass surface. Large amounts of glycerin and ferric chloride contained therein inhibit ammonium bifluoride from diffusing, resulting in a remarkably lowered etching reactivity. Such glass etching composition has very high viscosity, and therefore cannot provide a precise pattern and design on the glass surface. In addition, a large amount of ammonium bifluoride may cause health damages. Accordingly, the glass etching composition cannot be conveniently used, and is not suitable for daily application, but for special application.
The present invention provides a glass etching composition, which solves the above mentioned problems, and also provides a frosting method therewith for a glass surface.
According to the present invention, a glass etching liquid composition comprising 1 to 10 weight/volume % (hereinafter referred to as w/v %), preferably 2 to 5 w/v % of fluoride, 20 to 80 volume/volume % (hereinafter referred to as v/v %), preferably 20 to 50 v/v % of water and 20 to 80 v/v %, preferably 50 to 80 v/v % of water-miscible organic solvent is provided.
The glass etching composition is gelled by adding a gelling agent.
The glass etching composition gelled or not gelled may further contain sucrose as a stabilizer.
The glass etching composition gelled or not gelled may further contain surfactants.
The glass etching composition gelled or not gelled may further contain at least one of acetic acid, citric acid and phosphoric acid, and a buffer thereof to adjust a pH.
The glass etching composition gelled or not gelled may be colored with a dye.
The fluoride in the glass etching composition gelled or not gelled is at least one compound selected from the group consisting of sodium fluoride, potassium fluoride, ammonium fluoride, sodium bifluoride, potassium bifluoride and ammonium bifluoride.
The water in the glass etching composition gelled or not gelled is selected from the group consisting of tap water, ion exchange water, distilled water, ground water, spring water, filtrate water and a mixture of two or more thereof.
The water-miscible organic solvent in the glass etching composition gelled or not gelled is at least one compound selected from glycerin, and the group consisting of a glycol such as methyl glycol, ethyl glycol, methylene glycol, ethylene glycol, propylene glycol, dimethylene glycol, diethylene glycol, dipropylene glycol, polymethylene glycol and polyethylene glycol, and the group consisting of a glycol ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobuthyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether and dipropylene glycol monobutyl ether, and the group consisting of a alcohol such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 1,2-ethane diol, 1,2-propane diol, 1,3-propane diol, 1,4-butane diol, 1,2,3-propane triol, 1,2,6-hexane triol and sorbitol.
The gelling agent in the glass etching composition gelled is at least one compound selected from the group consisting of hydroxypropyl cellulose, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, sodium arginate, arabic gum, tragacanth gum, xanthum gum, bentonite, veegum, gelatin, bengl gelatin, polyacrylate, polyacryl amide, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, an acrylate polymer, an isobutyl maleic acid copolymer, an acrylic acid/methacrylic acid copolymer, an acrylic acid/maleic acid copolymer and variants thereof.
The surfactant in the glass etching composition gelled or not is at least one compound selected from the group consisting of an anionic surfactant such as dodecylbenzene sodium sulfonate, an alkylbenzene sodium sulfonate, lignine calcium sulfonate, a perfluoroalkyl sulfonate, a perfluoroalkyl carboxylate and a perfuloroalkyl phosphate, and the group consisting of an non-ionic surfactant such as polyoxyethylene acetyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleil ether, polyoxyethylene stearyl ether, a polyoxyethylene alkyl ether, polyoxyethylene octyl-phenyl ether, polyoxyethylene nonylphenyl ether, sorbitan laurate, sorbitan palmitate, sorbitan oleate, sorbitan stearate, polyoxy-ethylene sorbitan monolaurate, polyoxyethylene sorbitan mono-palmitate, polyoxyethylene sorbitan monooleate and polyoxy-ethylene sorbitan monostearte, and the group consisting of an ampholytic surfactant such as a dimethylalkyl betain, a alkyl glycine, amide betaine, imidazoline, a perfluoroalkylamino sulfonate, a perfluoroalkyl betaine, and the group consisting of a cationic surfactant such as octadecyldimethylbenzylammonium chloride, a alkyldimethylbenzylammonium chloride, tetradecyldi-methylbenzylammonium chloride, dioleyldimethylammonium chloride, octadecyl trimethylammonium chloride, a alkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethyl-ammonium chloride, a octadecylamine actate, a hexadecylamine acetate, a perfluoroalkyltrimethylammonium salt and a perfluoro-alkyl quaternary ammonium salt.
The glass etching liquid composition of the present invention is preferably used to frost glass articles. After cleaning on the glass surface by flushing with a cleaning agent and wiping the glass dry, the glass surface where etching is not required is optionally protected by masking. The glass is coated with the glass etching composition by immersing or spraying. After completion the frosting treatment, the glass is cleaned again with water to remove the residual etching composition and the masking therefrom.
The glass etching gel composition of the present invention is preferably used to frost glass articles. After cleaning on the glass surface by flushing with the cleaning agent and wiping the glass dry, the glass surface where etching is not required is optionally protected by masking. The glass is coated with the glass etching composition by immersing, applying with a brush or squeezing from a tube. After completion the frosting treatment, the glass is cleaned again with water to remove the residual etching composition and the masking therefrom.
In the frosting method for a glass surface, the cleaning agent is selected from water, a soap, a household cleanser or a household detergent.
In the frosting method for a glass surface, the masking is made by an oily pen, an oily paint, a resin paint, an acrylic paint, a masking tape, a seal, a silk screen printing method or other printing methods.